Fireproof, waterproof, flexible sheeting resistant to penetration by chemical warfare vesicant agents



Patented Aug. 5, 1952 smsrn'oor, WATE .SHEETING RESIST nrnoorjrpnxmtn I; j

ANT T PENETRA TION BY CHEMICAL WARFARE VESI CANT AGENTS William H.

States Army, assignors America as represented by the Secretarynf War Di W s p l ati n August 1 1943, Serial N0.499,246

(emanate: the act of-March s, 1883-, as

amended April so, 1928; 370 o. G. 757) The invention described herein maybe manufactured and used by or for the Government, for governmental purposes, without the payment to us of any royalty thereon.

This invention relates, generally, to sheet material resistant to chemical warfare vesicant agents, and which is also fireproof and waterproof. The invention relates particularly to such sheet material formed by applying one 'or more layers of a coating composition comprising as its essential ingredients, a proteinaceous material and an ammonium 'alkyl or alkylolamino phosphate, together with certain other ingredients as will be described hereinafter.

The object of this invention, generally stated, is to provide sheet material in the form of coated papers and fabrics which is resistant to chemical warfare vesicant agents, capable of being produced on a quantity production basis from inexpensive readily available materials, flexible at low temperatures, not subject to blocking or becoming sticky at relatively high temperatures, and which is fireproof and waterproof to relatively high degrees. This material is particularly useful in war-time for the manufacture of such articles as military capes to protect individuals against vesicant spray from airplanes, and to serve as protective covering for materiel. The

, sheeting material of this invention also has many commercial uses such as for making emergency raincoats, waterproof curtains, greaseproof wrappings, fireproof curtains and decorations, fireproof insulation, and the like.

More specific objects of this invention will be obvious, and certain others will be apparent from the following detailed description thereof.

Briefly stated, the invention consists in applying to a base sheet, such as a long-fibered-paper of the kraft type, cellophane, or fabrics, one or more layers of a coating composition containing as its essential ingredients a proteinaceous material and an ammonium alkyl or alkylolamino phosphate, and certain otheringredients such as a plasticizing material, and a solvent. If desired, the coating may be finally overcoated with a thin plasticized layer of a water-resistant lacquer or sheet which will adhere thereto. v

For a more complete understanding of the nature and scope of this invention, reference may be had to the following detailed description thereof setting forth by way of illustration certain specific formulas and embodiments.

The proteinaceous materials used in the coating compositions may be casein, glue, soybean Aiken and Albert L. James, United to the United States of protein (alpha) and mazein (zein), and the like. It has been found that certain ammonium alkyl and alkylolamino phosphates serve in the coating compositions not only as fireproofing agents but also as plasticizers, makingpossible the reduction or elimination of the amount of hygroscopic, polyhydroxy alcohols such as glycerine, sorbitol, and triethylene glycol, whichserve as plasticizing agents.

By the term phosphate" it is intended to include the salt of any one of the phosphoric or phosphorous acids, including ortho-phosphoric acid, meta-phosphoric acid, P m-phosphoric acid, hypo-phosphoric acid, phosphorous acid, and hypo-phosphorous acid. The phosphate radicals of these different phosphoric and phosphorous acids are more or less equivalent for the purposes of this invention.

The three following examples give the formulas in parts by weight of coating compositions constituting specific embodiments of this invention in which casein constitutes the proteinaceous material:

Example 12;

100 parts casein 10-20 parts ammonium hydroxide 3-6 parts formalin 100 parts monoethanolamineethyl phosphate As desired, water 5 Emarmple 2 100 parts casein 15 parts ammonium hydroxide 6 parts formalin -150 parts monoethanolamine ethyl phosphate 700 parts water Example 3' parts casein 15 parts ammonium hydroxide 6 parts formalin 50-125 parts monoethanolamineethyl phosphate -75 parts glycerine 700 parts water in the three above examples in placeof the monoethanolamine ethyl phosphate.Likewise,1mono-ft ethanolamine phosphate can beused asthe phosjphate ingredient in the three above examples. This latter material makes a satisfactory fireproof coating but does not make as good a plas-l ticizer as the ethyl and butyl'monoethanolamine phosphates. h

The six following examplesgive the formulas in parts by weight of coating compositions form- 4 Example 9 100 parts zein 200-25 parts glycols 25-200 parts a phosphate selectedfrom the group consisting of ammonium ethyl phosphate, ammonium butyl phosphate, monoethanolamine ethyl phosphate, monoethanolamine butyl, phosphate, and monoethanolamine phosing additional specific embodiments of this'iii-f vention wherein glue, soybean protein-(alpha), mazein-zein, and zein serve as the roteina ous; materials:

100 partsg-iue (hide or bone) 5200-50 parts aphosphate selecte'd fromthe group consisting 'of 'ammoniu'm' ethyl phosphate, ammonium butyl -phos'phate monoethanolamine ethyl phosphate, *monoethanolamine :butyl phosphate, and monoethariolamin'e' phosphate.

100-1000 parts water Example 5 ioo'barts' mumae orbone): j 1 200-50 p'arts"a hygroscopic, polyhydroxy alcohol selected from the group consisting of glycerine,

" sorbitol, and theglyc'ols; 1

50-200 parts a phosphate selected from the group 1 consisting of ammonium ethyl phosphate, ammonium butyl phosphate; m'onoethanolamine ethyl phosphate, monoethanolamine' butyl phosphate, and monoethanolamine phosphate 100-1000 parts water 1 Example 6 50-200 parts a phosphate selected from the. group 1 consisting of ammonium ethyl phosphate,

ammonium butyl phosphate,. vmonoethanolamine ethyl phosphate, monoetha'nolamine butyl 'monoethanolaminet, mixed slowly and heat is evolved making cooling ,phate. I 300-1000 parts ethyl alcohol 65% to 92% -The"compositions of Examples 4 through 9 may be prepared in accordance with the manner outlined above for the compositions given in Examples 1, 2and. 3.

' In each of the nine specific coating compositions given above, the proteinaceous material may be wholly or partially replaced by other proteinaceous materials, such as any one of those given above. Likewise, the phosphate component in the nine above specific examples, may be partially or wholly replaced by other phosphates of the same class. V

The phosphates of the class satisfactory for use in the coating compositions of this invention may be prepared by reacting in the proper proportions the desired phosphoric acid derivatives with ammonia or the desired aminoderivatives. For 'example, monoethanolamine ethyl phosphate is prepared by reacting 118, parts of the ethyl phosphoric acid with 72.5,parts of These two materials are necessary. The resultingmixture should be neutral to litmus when mixed with water. Monoethanolamine-butyl phosphate is prepared in the same manner by reactingtogether 100 parts of butyl phosphoric acid and 54 parts of monoethanolamine. Likewise, ethyl phosphate is prepared by reacting together the proper proportions of ammonia and ethyl phosphoric acid, ammonium butyl phosphate is prepared by reacting ammonia and butyl phosphoric acid, and monoethanolamine phosphate is prepared by reacting together monoethanolamine and, phosphoric acid;

In the above nine specific examples, water and ethylialcohol were used as. the solvent component of the coating compositions.-Itj will be understood that in place of ethyl alcohol other low alcohols may be-used such asmethyl alcohol,

phosphate, and monoethanolamine phosphate *propyl alcohol and butyl alcohol;

500-1000 parts water Example 7 7 Example 8 100 parts-mazein-zein w 25-200 parts a phosphate selected from'the group consisting 'ofammonium -ethyl phosphate, 70

ammonium butyl phosphate, monoethanolamine ethyl phosphate, "mgnoethanolamine butyl phosphate, andmonoethanolamine phosphate 300-1000 parts ethyl alcohol 65% to 92%;

The ammonium ethyl phosphates, ammonium butyl phosphates, and monoethanolamine ethyl and butyl phosphates, :are all n'on-crystallizing, hygroscopic substances, which give firepro'ofness.

Monoethanolamine phosphate is also non-crystallizing, but is phosphates.

As stated/the presently preferred material on which'the coating compositions of this invention are applied is alo'ng-fibered paper exemplified by the grade generally known a s'kraftpaper. This type of paper is comparable to tough wrapping paper and may have a weight of from 10 to pounds per ream. However, cellophane also serves as a satisfactory base, as well as cernot as hygroscopic as the other tain fabrics such as cotton clot The'coating compositions may be applied to the base sheetby conventional coating procedure. For example, the coatings maybe applied on a large scale by means of the standard coating equipment now used in paper mills 'for the manufacture of coated, paper. Oneor more layers of the coating compositions may be applied on one orboth sides, with one-layer beingof one type and another layer being of another type. Of course, the more layers applied to the sheet base, the greater will be the protection given to vesicant agents, and the greater will be the degree of fireproofness and waterproofness obtained.

The layers of the coating compositions of this invention may be overcoated with a thin plasticized layer of a water-resistant lacquering solution or sheet which will adhere thereto. Such an overcoating is particularly desirable where the sheeting material is to be exposed outdoors for extended periods. For example, the coated sheets may be overcoated with a thin layer of lacquer material such as ethyl cellulose, cellulose acetate, or nitrocellulose. One specific example of a sheet overcoating material is a nitrocellulose lacquer plasticized with dibutyl sebacate, or the various pelargonates plasticizers.

Desired pigment materials may be incorporated in the protein-phosphate coatings, or in the overcoating lacquers, or both.

When glue is used as the proteinaceous constituent in the coating compositions, it is preferably cured by admixture with, dipping in, or exposure to, formaldehyde fumes in accordance with known procedure for rendering glue resistant to water.

The sheet materials made according to the invention are characterized by being flexible at temperatures as low as 0 F., and by not blocking (sticking together when tiered) up to 150 F. The sheeting materials are resistant to liquid vesicants, such as mustard gas, nitrogen mustard, and lewisite, up to several hours.

By the expression fireproof, it is intended to designate that degree of non-infiammability such that the sheeting materials of this invention will not sustain combustion by themselves after being ignited and the external flame is removed, and when the ambient atmosphere is at room temperature.

By the expression waterproof, it is intended to designate that degree of water resistance ordinarily associated with such materials as shower curtains, raincoats, oilcloths, and the like.

Since certain further changes, modifications, and substitutions may be made in the foregoing embodiments, formulas, and methods of preparations, without departing from the scope of the invention, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

We claim as our invention:

I 1. A fireproof, waterproof, flexible sheeting resistant to penetration by chemical warfare vesicant agents which comprises a water absorb ent, gas absorbent cellulosic sheet having applied thereto as a coating at least one layer of a composition comprising an ammoniated water solution of formalin-cured casein, and a fireproofing and plasticizing agent of the class consisting of monoethanol phosphate, monoethanol ethyl phosphate, monoethanol butyl phosphate, ammonium ethyl phosphate, and ammonium butyl phosphate, the casein and fireproofing and plasticizing agent being present in the ratio of 100 parts of the former to -150 parts of the latter, the casein having approximately from 3 to 6 parts of formalin incorporated with each parts thereof and the solvent having therein approximately 10 to 20 parts of ammonium hydroxide per 700 parts thereof.

2. A fireproof, waterproof, flexible sheeting resistant to penetration by chemical warfare vesicant agents which comprises a water absorbent, gas absorbent cellulosic sheet having applied thereto as a coating at least one layer of a composition comprising an ammoniated water solution of formalin-cured casein, glycerine, and a fireproofing and plasticizing agent of the class consisting of monoethanol phosphate, monoethanol ethyl phosphate, monoethanol butyl phosphate, ammonium ethyl phosphate, and ammonium butyl phosphate, the casein, glycerine, and fireprocfing and plasticizing agent being present in the ratio of 100 parts of the casein to 50-125 parts of the said agent, and parts to '75 parts of glycerine respectively as to the said agent, the casein having approximately from 8 to 6 parts of formalin incorporated with each 100 parts thereof and the solvent having therein approximately 10 to 20 parts of ammonium hydroxide per 700 parts thereof.

3. A fireproof, waterproof, flexible sheet according to claim 1 wherein the fireproofing and plasticizing agent is monoethanolamine ethyl phosphate.

4. A fireproof, waterproof, flexible sheet according to claim 1 wherein the fireproofing and plasticizing agent is ammonium ethyl phosphate.

5. A fireproof, waterproof, flexible sheet according to claim 2 wherein the fireproofing and plasticizing agent is monoethanolamine ethyl phosphate.

WILLIAM H. AIKEN. ALBERT L. JAMES.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 126,851 Taylor May 14, 1872 1,966,271 Twiss July 10, 1934 2,032,605 Whitehead Mar. 3, 1936 2,193,818 Kajita Mar. 19, 1940 2,262,634 Cobbs Nov. 11, 1941 2,338,664 Nadeau Jan. 4, 1944 FOREIGN PATENTS Number Country Date 3,262 Great Britain Dec. 22, 1900 

1. A FIREPROOF, WATERPROOF, FLEXIBLE SHEETING RESISTANT TO PENETRATION BY CHEMICAL WARFARE VESICANT AGENTS WHICH COMPRISES A WATER ABSORBENT, GAS ABSORBENT CELLULOSIC SHEET HAVING APPLIED THERETO AS A COATING AT LEAST ONE LAYER OF A COMPOSITION COMPRISES AN AMMONIATED WATER SOLUTION OF A FORMALIN-CURED CASEIN, AND A FIREPROOFING AND PLASTICIZING AGENT OF THE CLASS CONSISTING OF MONOETHANOL PHOSPHATE, MONOETHANOL ETHYL PHOSPHATE, MONOETHANOL BUTYL PHOSPHATE, AMMONIUM ETHYLL PHOSPHATE, AND AMMONIUM BUTYL PHOSPHATE, THE CASEIN AND FIREPROOFING AND PLASTICIZING AGENT BEING PRESENT IN THE RATIO OF 100 PARTS OF THE FORMER TO 50-150 PARTS OF THE LATTER, THE CASEIN HAVING APPROXIMATELLY FROM 3 TO 6 PARTS OF FORMALIN INCORPORATED WITH EACH 100 PARTS THEREOF AND THE SOLVENT HAVING THEREIN APPROXIMATELY 10 TO 20 PARTS OF AMMONIUM HYDROXIDE PER 700 PARTS THEREOF. 